{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,7,30]],"date-time":"2026-07-30T10:31:51Z","timestamp":1785407511390,"version":"3.56.0"},"reference-count":50,"publisher":"MDPI AG","issue":"8","license":[{"start":{"date-parts":[[2026,4,20]],"date-time":"2026-04-20T00:00:00Z","timestamp":1776643200000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100006769","name":"Russian Science Foundation","doi-asserted-by":"publisher","award":["24-73-00055"],"award-info":[{"award-number":["24-73-00055"]}],"id":[{"id":"10.13039\/501100006769","id-type":"DOI","asserted-by":"publisher"}]},{"award":["24-73-00055"],"award-info":[{"award-number":["24-73-00055"]}],"id":[{"id":"https:\/\/ror.org\/03y2gwe85","id-type":"ROR","asserted-by":"publisher"}]},{"name":"Ministerio de Ciencia, Innovaci\u00f3n y Universidades of Spain","award":["MCIU\/AEI\/10.13039\/501100011033"],"award-info":[{"award-number":["MCIU\/AEI\/10.13039\/501100011033"]}]},{"award":["MCIU\/AEI\/10.13039\/501100011033"],"award-info":[{"award-number":["MCIU\/AEI\/10.13039\/501100011033"]}],"id":[{"id":"https:\/\/ror.org\/05r0vyz12","id-type":"ROR","asserted-by":"publisher"}]},{"name":"FEDER, UE"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["IJMS"],"abstract":"<jats:p>A series of Group 10 metal dithiocarbonate complexes [M(S2COiPr)2] (M = Ni 1, Pd 2, Pt 3) was prepared following procedures from the literature and cocrystallized with the ditopic \u03c3\/\u03c0-hole donor 1,4-diiodotetrafluorobenzene. Single-crystal X-ray diffraction revealed a consistent I\u00b7\u00b7\u00b7S halogen bonding motif alongside a remarkable diversity in metal-involving interactions across the Ni\u2013Pd\u2013Pt triad. While nickel(II) exhibits strong electrophilic M\u00b7\u00b7\u00b7S semicoordination, the palladium(II) center displays ambiphilic behavior, and platinum(II) acts exclusively as a nucleophile via \u03c0-hole\u00b7\u00b7\u00b7M bonding. Comprehensive density functional theory studies, including molecular electrostatic potential (MEP) mapping, quantum theory of atoms in molecules\/noncovalent interaction plot analyses, and energy decomposition analysis, were used to quantify this competitive balance. The results demonstrate that the increasing nucleophilicity from Ni to Pt, supported by shifting MEP minima and stronger \u03c0-hole stabilization energies, dictates the preference for nucleophilic over electrophilic metal-centered contact.<\/jats:p>","DOI":"10.3390\/ijms27083668","type":"journal-article","created":{"date-parts":[[2026,4,20]],"date-time":"2026-04-20T13:22:47Z","timestamp":1776691367000},"page":"3668","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Interplay of Semicoordination and \u03c0-Hole Bonding: The Case of Cocrystals of Group 10 (Ni, Pd, Pt) Dithiocarbonate Complexes with 1,4-Diiodotetrafluorobenzene"],"prefix":"10.3390","volume":"27","author":[{"given":"Marina A.","family":"Stozharova","sequence":"first","affiliation":[{"name":"Institute of Chemistry, St. Petersburg State University, Universitetskaya Nab. 7\/9, St. Petersburg 199034, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Vitaly V.","family":"Suslonov","sequence":"additional","affiliation":[{"name":"Institute of Chemistry, St. Petersburg State University, Universitetskaya Nab. 7\/9, St. Petersburg 199034, Russia"},{"name":"\u201cTMH TM\u201d LLC., Nepokoryonnykh Av. 47, St. Petersburg 195220, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0827-8504","authenticated-orcid":false,"given":"Rosa M.","family":"Gomila","sequence":"additional","affiliation":[{"name":"Departament de Qu\u00edmica, Universitat de les Illes Balears, Crta de Valldemossa km 7.5, 07122 Palma de Mallorca, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7840-2139","authenticated-orcid":false,"given":"Antonio","family":"Frontera","sequence":"additional","affiliation":[{"name":"Departament de Qu\u00edmica, Universitat de les Illes Balears, Crta de Valldemossa km 7.5, 07122 Palma de Mallorca, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2982-3804","authenticated-orcid":false,"given":"Anastasiya A.","family":"Eliseeva","sequence":"additional","affiliation":[{"name":"Institute of Chemistry, St. Petersburg State University, Universitetskaya Nab. 7\/9, St. Petersburg 199034, Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2026,4,20]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"454","DOI":"10.1021\/acs.accounts.7b00514","article-title":"Ambiphilic Molecules: From Organometallic Curiosity to Metal-Free Catalysts","volume":"51","author":"Fontaine","year":"2018","journal-title":"Acc. 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